Solvent composition and water-repellent/oil-repellent composition using the same

ABSTRACT

A non-flammable water-repellent/oil repellent composition containing a fluorine containing-polymer and a solvent containing at least 40% by weight of a non-flammable perfluoro organic compound.

This application is a division of application Ser. No. 08/842,031, filed Apr. 23, 1997, now U.S. Pat. No. 5,954,990, which is a division of application Ser. No. 08/487,673, filed Jun. 7, 1995, abandoned, which is a continuation of application Ser. No. 08/371,213, filed Jan. 11, 1995, now U.S. Pat. No. 5,458,692, which is a division of application Ser. No. 07/956,076, filed Oct. 2, 1992, now U.S. Pat. No. 5,403,514.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a novel nonflammable solvent composition having excellent characteristics as a solvent which can take the place of 1,1,2-trichloro-1,2,2-trifluoroethane (hereinafter abbreviated to "CFC-113"), and furthermore, it relates to a fluorine-based water-repellent/oil-repellent composition using the above-mentioned solvent composition and having water-repellent/oil-repellent properties, lubricating properties, mold release properties and the like.

2. Related Background Art

Most of chlorofluorocarbons (hereinafter abbreviated to "CFCs") are less toxic, incombustible and chemically stable, and various kinds of CFCs having different boiling points are available and therefore they have been utilized in many industrial fields. Above all, CFC-113 has been used as a degreasing solvent, a dispersant and a diluting solvent for a plastic material, a part of rubber materials and various composite materials by the utilization of its specific chemical characteristics.

In recent years, ozone holes which are due to unusual changes of earth environment have been discovered, and it has been elucidated that its main cause is organic chlorine-based compounds. Particularly chemically stable CFC-113 has a long life in the troposphere, and it diffuses and reaches the stratosphere. In the stratosphere, CFC-113 gives rise to photolysis under the influence of sunbeams to generate chlorine radicals. The thus generated chlorine radicals combine with ozone, so that an ozone layer is broken. Accordingly, the use of the organic chlorine-based compounds inclusive of the CFCs will be globally restricted and forbidden in the future. Among others, CFC-113 has a high ozone destruction coefficient, and hence its prompt replacement is desired and a severe schedule of reducing the employment of CFC-113 is justified.

SUMMARY OF THE INVENTION

An object of the present invention is to provide a novel solvent composition replaceable with CFC-113 which has been heretofore used in such circumstances.

Another object of the present invention is to provide a solvent composition suitable as a degreasing solvent for various substrates.

Still another object of the present invention is to provide a water-repellent/oil-repellent composition suitable as a modifier for the surfaces of various substrates.

The present invention for achieving the above-mentioned objects is directed to a nonflammable solvent composition containing 40% by volume or more of non-flammable perfluoro organic compound, and a nonflammable water-repellent/oil-repellent composition containing a fluorine-containing polymer and a solvent containing 40% by weight or more of a non-flammable perfluoro organic compound.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The reasons why CFC-113 has often been used as a degreasing solvent are

(a) that it has a suitable solubility to various soils and oils,

(b) that it is excellent in chemical stability, and there is no worry of decomposition and the like,

(c) that it is less toxic and has neither a flash point nor an ignition point, and thus its operational safety is high, and

(d) that its polarity is low and it does not damage various plastic materials.

Therefore, in order to take the place of CFC-113, similar characteristics are required. Nowadays, as the Hydrochlorofluorocarbons (HCFC), there have been developed hydrochlorofluorocarbons such as 1,1-dichloro-2,2,2-trifluoroethane (hereinafter abbreviated to "HCFC-123"), 1-fluoro-1,1-dichloroethane (hereinafter abbreviated to "HCFC-141b"), 1,1-dichloro-2,2,3,3,3-pentafluoropropane (hereinafter abbreviated to "HCFC-225ca") and 1,3-dichloro-1,1,2,2,3-pentafluoropropane (hereinafter abbreviated to "HCFC-225cb"), and their substitution has been investigated.

However, most of these Hydrchlorofluorocarbons have high solubility to various oils and fats but tend to attack substrates, particularly, general-purpose plastics such as acrylic resins and ABS resins, and therefore they are not considered to be all-round substitutes of CFC-113.

In order to satisfy the above-mentioned necessary properties, much attention is paid to perfluoro organic compounds having less chemical attack properties, and various kinds of solvent compositions have been intensively investigated. As a result, the present invention has been attained. That is, the solvent composition which can be used in the present invention contains a non-flammable perfluoro organic compound which has an extremely low polarity and no degreasing ability and which does not damage various substrates at all. In view of requirements of having no flash point, having a high vapor pressure, having a high chemical stability and having a reduced chemical attack to various materials, there can be suitably used perfluoroalkanes, perfluorocycloalkanes, perfluoro ethers, perfluoro cycloethers and the like as the perfluoro organic compounds which are used in the present invention.

Furthermore, the perfluoro organic compounds which can be used in the present invention preferably have a vapor pressure of 30 Torr or more at 25° C.

Typical examples of the perfluoro organic compounds include perfluoropentane (C₅ F₁₂), perfluorohexane (C₆ F₁₄), perfluoroheptane (C₇ F₁₆) perfluorooctane (C₈ F₁₈), perfluorocyclohexane (C₆ F₁₂), perfluorocycloheptane (C₇ F₁₄), perfluoro(alkylcyclohexane) (C₇ F₁₄ and C₈ F₁₆) and perfluoro(2-butyltetrahydrofuran) (C₈ F₁₆ O). The content of each of these perfluoro organic compounds is preferably 40% by volume or more based on the volume of the solvent composition of the present invention. When the content of the perfluoro organic compound is less than the above-mentioned amount, a flash point appears, and in the case that the compound is used in the form of a mixture with another flammable organic compound, the chemical attack of the flammable organic compound on products takes place inconveniently.

When the solvent composition of the present invention is used as the above-mentioned degreasing solvent, an organic compound having a degreasing power, particularly a flammable organic compound is added to the solvent composition.

This flammable organic compound having the degreasing power is required

(1) to be miscible with the perfluoro organic compound,

(2) to have a suitable dissolving power (the degreasing power) to various soils and oils, and

(3) to have a reduced chemical attack to products (particularly general-purpose plastics).

Examples of the particularly preferable organic compound which can meet the above-mentioned requirements include ether compounds, alkanes and cycloalkanes.

Preferable typical examples of the ether compounds include compounds represented by the formula

    R.sub.1 --O--R.sub.2

wherein R₁ is C_(n) H_(2n+1) or --Si(CH₃)₃, R₂ is C_(m) H_(2m+1) or --Si(CH₃)₃, and n and m meet 1≦n, m≦4, and 2≦n+m≦6.

Preferable typical examples of the alkanes and cycloalkanes include compounds represented by the formulae

    C.sub.p H.sub.2p+2 and C.sub.q H.sub.2q

wherein p and q meet 5≦p and q≦8.

In order to satisfy the above-mentioned requirements (2) and (3), a particularly preferable embodiment is to use an organic compound having a solubility parameter (an SP value) of 7.5 or less. The SP values can be directly calculated from evaporation latent heat or vapor pressure, but in this specification, literature values mentioned in POLYMER HANDBOOK, 2nd Edition are employed and they are as follows (the values in parentheses were calculated in accordance with an intermolecular attraction constant method of Small). Preferable typical examples of such organic compounds are as follows:

    ______________________________________                                         n-pentane             SP value = 7.0 (7.2)                                     n-hexane              SP value = 7.3 (7.3)                                     2-methylpentane (isohexane)                                                                          SP value = (7.1)                                         2-methylhexane (isoheptane)                                                                          SP value = (7.2)                                         2,2,4-trimethylpentane (isooctane)                                                                   SP value = (6.8)                                         hexamethyldisiloxane (C.sub.7 H.sub.17 OSi.sub.2)                                                    SP = (6.0)                                               diethyl ether (C.sub.4 H.sub.10 O)                                                                   SP = 7.4 (7.3)                                           diisopropyl ether (C.sub.6 H.sub.14 O)                                                               SP = 7.0 (6.9)                                           methyl tert-butyl ether (C.sub.5 H.sub.12 O)                                                         SP = (7.2).                                              ______________________________________                                    

Furthermore, the solvent composition of the present invention can be also suitably used as a solvent composition for a water-repellent/oil-repellent agent which can modify the surfaces of substrates, i.e., can protect the substrates from contamination and impart water-repellent/oil-repellent properties to them.

As the solvent for the water-repellent/oil-repellent agent, 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) has been overwhelmingly used for the reasons of the solubility of a polymer, safety, stability and the like. As other examples of the solvent, there have been used toluene, ethyl acetate and 1,1,1-trichloroethane, but these solvents tend to damage the substrates to be treated. Therefore, restriction is put on the selection of the substrates. In addition, most of these solvents are flammable, and therefore safety and the like are insufficient.

According to the present invention, there can be provided a non-ODC (Ozone Depletion Chemicals) type all-round water-repellent/oil-repellent composition which is free from a flash point and which is applicable to the various substrates without the restriction, by the use of a solvent composition containing 40% by weight or more of the above-mentioned non-flammable perfluoro organic compound as a solvent component of the water-repellent/oil-repellent composition.

In order to develop the non-ODC type all-round water-repellent/oil-repellent composition of the present invention which is applicable to the surfaces of the various substrates to be treated, a solute and a solvent are required to have the following characteristics.

Solute:

(a) To have a functional group for giving a sufficiently low surface energy, and

(b) to give a sufficient adhesive strength to the various substrates,

Solvent:

(a) To have selective solubility only to the solute, and neither to dissolve nor to swell other materials,

(b) to be less toxic, to have neither a flash point nor an ignition point, and thus to have high operational safety, and

(c) to have a high vapor pressure and a high drying rate.

For the purpose of obtaining the water-repellent/oil repellent composition which can meet all of the above-mentioned necessary characteristics, solvent mixtures have been intensively investigated, and as a result, the present invention has been attained.

The solute of the water-repellent/oil repellent composition which is used in the present invention is preferably a fluorine-containing polymer having a long-chain perfluoroalkyl group of C₆ F₁₃ or more as a functional group, and the polymer preferably contains 40 mole % or more of the fluorine-containing vinyl monomer so as to be highly fluorinated. The perfluoroalkyl group of C₆ F₁₃ or more as the functional group is particularly excellent in oil-repellency. In addition, also in the case that the polymer contains 40 mole % or more of the fluorine-containing vinyl monomer, the polymer is particularly excellent in oil-repellency. Typical examples of the solute which can be used in the present invention are as follows.

Homopolymer of 2-(perfluorooctyl)ethyl acrylate, homopolymer of (perfluoroheptyl)methyl methacrylate, homopolymer of 2-(N-ethylperfluorooctasulfoamido)ethyl acrylate, 2-(perfluorohexyl)ethyl methacrylate (60 mole %)/methyl methacrylate (30 mole %)/2-hydroxyethyl methacrylate (10 moles) copolymer, 2-(perfluorooctyl)ethyl acrylate (70 moles)/benzyl methacrylate (25 mole %)/2-hydroxyethyl methacrylate (5 mole %) copolymer, and 2-(perfluoroisononyl)ethyl acrylate (50 mole %)/vinyl acetate (30 mole %)/methyl methacrylate (10 mole %)/2-hydroxyethyl methacrylate (10 mole %) copolymer.

When it is desired to obtain the uniform and flat film, each of the above-mentioned solutes is preferably used in the range of from 0.01% to 5% by weight, more preferably in the range of from 0.05% to 1% by weight, based on the weight of the total components. A solute concentration of 0.01% by weight or more is particularly preferable in that the film having the sufficient oil-repellency can be formed, and at a solute concentration of 5% by weight or less, the uniform film can be obtained due to the salvation of the solute.

Furthermore, as the solvent composition for dissolving the above-mentioned solute which can be used in the water-repellent/oil-repellent composition of the present invention, a solvent for extinguishing a flash point of the total water-repellent/oil-repellent composition of the present invention and for relieving the damage to the substrate is preferable. In fact, the above-mentioned solvent composition of the present invention is suitable. In addition, usual organic solvents and chlorine-based solvents can be also used together with the solvent composition, depending upon kinds of solute and other additives.

Examples of the solvent which can be used together with the solvent composition of the present invention include fluorine-containing solvents, for example, perfluorocarboxylic acid derivatives such as methyltrifluoro acetate, ethyltrifluoro acetate and butylpentafluoro propionate; fluorine-based benzene derivatives such as hexafluorobenzene, pentafluorobenzene, benzotrifluoride and bistrifluoromethylbenzene; fluorine-containing alcohols such as trifluoroethanol, pentafluoropropanol and hexafluoroisopropanol; and hydrochlorofluorocarbons such as HCFC-123, HCFC-141b and HCFC-225.

Optional additives can be added to the water-repellent/oil-repellent composition of the present invention, so long as it has no flash point.

The water-repellent/oil-repellent composition of the present invention can be applied by the use of brush coating, immersion, spin coating, roll coating or spray coating.

EXAMPLES

Now, the present invention will be described in detail in reference to examples.

    ______________________________________                                         Example 1                                                                      Perfluorohexane     55 vol %                                                   Diisopropyl ether   45 vol %                                                   Example 2                                                                      Perfluoropentane    50 vol %                                                   Diethyl ether       50 vol %                                                   Example 3                                                                      Perfluoroheptane    60 vol %                                                   Diisopropyl ether   40 vol %                                                   Example 4                                                                      Perfluorohexane     25 vol %                                                   Perfluoropentane    25 vol %                                                   Isooctane           50 vol %                                                   Example 5                                                                      Perfluorooctane     30 vol %                                                   Perfluoro(butyltetrahydrofuran)                                                                    20 vol %                                                   Isooctane           50 vol %                                                   Example 6                                                                      Perfluorohexane     60 vol %                                                   Methyl tert-butyl ether                                                                            40 vol %                                                   Example 7                                                                      Perfluorohexane     55 vol %                                                   Isohexane           45 vol %                                                   Example 8                                                                      Perfluorohexane     50 vol %                                                   Hexamethyldisiloxane                                                                               50 vol %                                                   Example 9                                                                      Perfluoropentane    20 vol %                                                   Perfluorohexane     30 vol %                                                   Methyl tert-butyl ether                                                                            25 vol %                                                   n-hexane            25 vol %                                                   Example 10                                                                     Perfluoropentane    20 vol %                                                   Perfluorohexane     20 vol %                                                   Diisopropyl ether   20 vol %                                                   Isooctane           40 vol %                                                   Comparative Example 1                                                          CFC-113                                                                        Comparative Example 2                                                          CFC-123                                                                        Comparative Example 3                                                          CFC-141b                                                                       Comparative Example 4                                                          CFC-225ca           50 vol %                                                   CFC-225cb           50 vol %                                                   Comparative Example 5                                                          Perfluorohexane     20 vol %                                                   Diisopropyl ether   80 vol %                                                   Comparative Example 6                                                          Perfluorohexane     30 vol %                                                   Diisopropyl ether   60 vol %                                                   ______________________________________                                    

In Table 1,there are comparably shown characteristics of the mixed solvent compositions in the above-mentioned ratios.

Plastic resistance

In order to confirm that bad influences such as dissolution and swelling to general-purpose plastics were not present, a swelling test was made. Test pieces of the used general plastics were as follows.

    ______________________________________                                         PMMA (acryl)      Delpet 80N (Asahi Chemical                                                     Industry Co., Ltd.)                                          PC (polycarbonate)                                                                               Panlight 1225 (Teijin                                                          Chemical Industry                                                              Co., Ltd.)                                                   ABS (acrylonitrile/buta                                                                          Saikorak EX120 (Ube Saikon                                   diene/styrene copolymer)                                                                         Co., Ltd.)                                                   POM (polyacetal)  Juracon M90 (Polyplastic                                                       Co., Ltd.)                                                   PS (polystyrene)  HT53 (Idemitsu                                                                 Petrochemicals                                                                 Co., Ltd.)                                                   Urethane rubber   Mirakutran E585 (Nippon                                                        Mirakutran Co., Ltd.)                                        ______________________________________                                    

The test was made by cutting each test material into test pieces having a size of 25×100, immersing them in each solvent composition of the above-mentioned examples and comparative examples for 1 hour, and then calculating weight changes after the immersion. The test pieces having a weight change of less than 0.1% by weight are represented by o, the test pieces of from 0.1% by weight to 1% by weight are represented by Δ, and the test pieces of 1% by weight or more are represented by x.

Flammability

The flammability was measured in accordance with JIS K2265 by the use of a tag sealing type automatic flash point test machine (ATG-4 type; Tanaka Science Instrument Co., Ltd.).

Degreasing Power

As model contaminants, there were selected a cutting oil (MC-W, Idemitsu Kousan Co., Ltd.) and an anticorrosive oil (Polybutene LV-7, Nippon Petrochemicals Co., Ltd.), and 10 μl of each oil were dropped on a slide glass (25×76×1) to prepare contaminated model products. Each model product was immersed in 50 ml of each solvent composition of the examples and the comparative examples, and then washed with at room temperature for 1 minute by means of an ultrasonic washing machine of 28 kHz and 100 W. After the model product was pulled up, a degreasing power was evaluated at a contact angle of pure water on the model product.

Drying Time

10 μl of each solvent composition were dropped on a slide glass, and a time which was taken until a weight change was not observed any more was measured.

ODP

Ozone depletion potentials (ozone destruction coefficient).

                                      TABLE 1                                      __________________________________________________________________________                              Flash                                                                             Degreasing                                                                            Drying                                      Plastic Resistance       Point                                                                             Power  Time                                        PMMA      PC                                                                               ABS                                                                               POM                                                                               PS                                                                               Urethane                                                                            [° C.]                                                                     MC-W                                                                               LV-7                                                                              [sec]                                                                              ODP                                     __________________________________________________________________________     Example 1                                                                            ◯                                                                      ◯                                                                    ◯                                                                     ◯                                                                     ◯                                                                    ◯                                                                       None                                                                              38  43  7  Absent                                  Example 2                                                                            ◯                                                                      ◯                                                                    ◯                                                                     ◯                                                                     ◯                                                                    ◯                                                                       None                                                                              36  41 -2  Absent                                  Example 3                                                                            ◯                                                                      ◯                                                                    ◯                                                                     ◯                                                                     ◯                                                                    ◯                                                                       None                                                                              39  44 19  Absent                                  Example 4                                                                            ◯                                                                      ◯                                                                    ◯                                                                     ◯                                                                     ◯                                                                    ◯                                                                       None                                                                              36  42 20  Absent                                  Example 5                                                                            ◯                                                                      ◯                                                                    ◯                                                                     ◯                                                                     ◯                                                                    ◯                                                                       None                                                                              36  41 50  Absent                                  Example 6                                                                            ◯                                                                      ◯                                                                    ◯                                                                     ◯                                                                     ◯                                                                    ◯                                                                       None                                                                              37  43  7  Absent                                  Example 7                                                                            ◯                                                                      ◯                                                                    ◯                                                                     ◯                                                                     ◯                                                                    ◯                                                                       None                                                                              35  40  6  Absent                                  Example 8                                                                            ◯                                                                      ◯                                                                    ◯                                                                     ◯                                                                     ◯                                                                    ◯                                                                       None                                                                              39  45 22  Absent                                  Example 9                                                                            ◯                                                                      ◯                                                                    ◯                                                                     ◯                                                                     ◯                                                                    ◯                                                                       None                                                                              36  41  7  Absent                                  Example 10                                                                           ◯                                                                      ◯                                                                    ◯                                                                     ◯                                                                     ◯                                                                    ◯                                                                       None                                                                              35  41 15  Absent                                  Comp. Ex. 1                                                                          ◯                                                                      ◯                                                                    ◯                                                                     ◯                                                                     ◯                                                                    ◯                                                                       None                                                                              36  41 28  Present                                 Comp. Ex. 2                                                                          ×                                                                            ×                                                                          ×                                                                           ×                                                                           ×                                                                          ×                                                                             None                                                                              35  40 10  Present                                 Comp. Ex. 3                                                                          ×                                                                            ×                                                                          ×                                                                           ×                                                                           ×                                                                          ×                                                                             None                                                                              36  41 10  Present                                 Comp. Ex. 4                                                                          ×                                                                            ◯                                                                    Δ                                                                           ◯                                                                     ◯                                                                    ×                                                                             None                                                                              36  42 31  Present                                 Comp. Ex. 5                                                                          ◯                                                                      ◯                                                                    ◯                                                                     ◯                                                                     ◯                                                                    ◯                                                                       10 35  40  7  Absent                                  Comp. Ex. 6                                                                          ◯                                                                      ◯                                                                    ◯                                                                     ◯                                                                     ◯                                                                    ◯                                                                       20 37  41  8  Absent                                  __________________________________________________________________________

Example 11

    ______________________________________                                         2-(perfluorooctyl)ethyl acrylate                                                                    0.1% by weight                                            (70 mole %)/benzyl methacrylate                                                (25 mole %)/2-hydroxyethyl                                                     methacrylate (5 mole %)                                                        copolymer                                                                      Perfluorohexane       90% by weight (*)                                        Bistrifluoromethylbenzene                                                                           9.9% by weight                                            ______________________________________                                          Note(*): This amount exceeds 40% by volume.                              

Example 12

    ______________________________________                                         Homopolymer of 2-(N-ethyl                                                                            0.25% by weight                                          per-fluoro octasulfoamide)ethyl                                                acrylate                                                                       Perfluoroheptane     99.75% by weight (*)                                      ______________________________________                                          Note(*): This amount exceeds 40% by volume.                              

Example 13

    ______________________________________                                         2-(perfluoroisononyl)ethyl                                                                           1% by weight                                             acrylate (50 mole %)/vinyl acetate                                             (30 mole %)/methyl methacrylate                                                (10 mole %)/2-hydroxyethyl                                                     methacrylate (10 mole %)                                                       copolymer                                                                      Perfluorohexane      50% by weight (*)                                         Perfluoro-2-         40% by weight (*)                                         butyltetrahydrofuran 40% by weight (*)                                         Pentafluorobenzene    9% by weight                                             ______________________________________                                          Note(*): Sum of these amounts exceeds 40% by volume.                     

Example 14

    ______________________________________                                         Homopolymer of       0.15% by weight                                           (perfluorohexyl)-ethyl                                                         acrylate                                                                       Perfluorohexane        60% by weight (*)                                       Perfluoroheptane       20% by weight (*)                                       Perfluorooctane        10% by weight                                           Benzotrifluoride     9.85% by weight                                           ______________________________________                                          Note(*): Sum of these amounts exceeds 40% by volume.                     

Example 15

    ______________________________________                                         (Perfluoroalkyl**)ethyl                                                                              0.3% by weight                                           acrylate (60 mole%)/methyl                                                     methacrylate (30 mole %)/                                                      hydroxyethylmethacrylate (10 moles)                                            copolymer                                                                      ______________________________________                                          (**The perfluoroalkyl group was a mixture of                                  4 F.sub.9 to C.sub.10 F.sub.21, and C.sub.8 F.sub.17 was the main               component.)                                                              

    ______________________________________                                         Perfluorooctane       45% by weight (*)                                        Perfluoro-2-          45% by weight (*)                                        butyltetrahydrofuran                                                           Bistrifluoromethylbenzene                                                                           9.7% by weight                                            ______________________________________                                          Note(*): Sum of these amounts exceeds 40% by volume.                     

Comparative Example 7

    ______________________________________                                         2-(perfluorooctyl)ethyl                                                                              0.1% by weight                                           acrylate (70 mole %)/benzyl                                                    methacrylate (25 mole %)/                                                      2-hydroxyethylmethacrylate (5 mole %)                                          copolymer                                                                      CFC-113              99.9% by weight                                           ______________________________________                                    

Comparative Example 8

    ______________________________________                                         2-(perfluorooctyl)ethyl                                                                             0.1 % by weight                                           acrylate (70 mole %)/benzyl                                                    methacrylate (25 mole %)/                                                      2-hydroxyethylmethacrylate                                                     (5 mole %) copolymer                                                           CFC-113               90% by weight                                            CFC-112              9.9% by weight                                            ______________________________________                                    

Comparative Example 9

    ______________________________________                                         2-(perfluoroisononyl)ethyl                                                                            1% by weight                                            acrylate (50 mole %)/vinyl acetate                                             (30 mole %)/methyl methacrylate (10                                            mole %)/2-hydroxyethyl methacrylate                                            (10 mole %) copolymer                                                          HCFC-225              99% by weight                                            ______________________________________                                    

Comparative Example 10

    ______________________________________                                         2-(perfluoroisononyl)                                                                                1% by weight                                             ethyl acrylate (50 mole %)/vinyl                                               acetate (30 mole %)/methyl                                                     methacrylate (10 mole %)/2-                                                    hydroxyethyl methacrylate                                                      (10 mole %) copolymer                                                          Pentafluoro propanol 99% by weight                                             ______________________________________                                    

Comparative Example 11

    ______________________________________                                         (Perfluoroalkyl**)ethyl                                                                              0.3% by weight                                           acrylate (60 mole %)/methyl                                                    methacrylate (30 mole %)/                                                      hydroxyethyl methacrylate                                                      (10 mole %) copolymer                                                          ______________________________________                                          (**The perfluoroalkyl group was a mixture of from                             4 F.sub.9 to C.sub.10 F.sub.21, and C.sub.8 F.sub.17 was the main               component.)                                                              

    ______________________________________                                         Ethyltrifluoro acetate                                                                                60% by weight                                           Perfluorohexane      39.7% by weight (*)                                       ______________________________________                                          Note(*): This amount does not exceed 40% by volume.                      

Comparative Example 12

    ______________________________________                                         (Perfluoroalkyl**)ethyl                                                                             0.3% by weight                                            acrylate (60 mole %)/methyl                                                    methacrylate (30 mole %)/                                                      hydroxyethyl methacrylate                                                      (10 mole %) copolymer                                                          ______________________________________                                          (**The perfluoroalkyl group was a mixture of from                             4 F.sub.9 to C.sub.10 F.sub.21, and C.sub.8 F.sub.17 was the main               component.)                                                              

    ______________________________________                                         HCFC-123           50% by weight                                               HCFC-141b          49.7% by weight                                             ______________________________________                                    

In Table 2, there are comparably shown characteristics of the oil-repellent compositions in the above-mentioned ratios.

Evaluation of Oil-Repellency

Each oil-repellent composition was applied onto an acrylic substrate (Delpet 80N; Asahi Chemical Industry Co., Ltd.), and the oil-repellency was then evaluated at a contact angle by hexadecane.

Plastic Resistance

In order to confirm that bad influences such as dissolution and swelling to general-purpose plastics were not present, a swelling test was made. As substrate materials to be used, there were selected PMMA (acryl), Delpet 80N (Asahi Chemical Industry Co., Ltd.), PC (polycarbonate), Panlight 1225 (Teijin Chemical Industry Co., Ltd.), ABS (acrylonitrile/butadiene/styrene copolymer), Saikorak EX120 (Ube Saikon Co., Ltd.), POM (polyacetal), Juracon M90 (Polyplastic Co., Ltd.), Urethane rubber, Mirakutran E585 (Nippon Mirakutran Co., Ltd.) and natural rubber. Each substrate having a size of 25×100×3 was immersed in each oil-repellent composition for 1 hour, and weight changes after the immersion were then calculated. The substrates having a weight change of less than 0.1% by weight are represented by o, the substrates of from 0.1% by weight to 1% by weight are represented by Δ, and the substrates of 1% by weight or more are represented by x.

Flammability

The flammability was measured in accordance with JIS K2265 by the use of a tag sealing type automatic flash point test machine (ATG-4 type; Tanaka Science Instrument Co., Ltd.).

Drying Time

10 μl of each solvent composition were dropped on a slide glass, and a time which was taken until weight change was not observed any more was measured.

                                      TABLE 2                                      __________________________________________________________________________            Plastic Resistance Oil-  Water-                                                                               Flash                                                                             Drying                                                  Rubber                                                                             Rubber                                                                             Repellency                                                                           Repellency                                                                           Point                                                                             Time                                                                               ODP                                      Acryl                                                                             PC                                                                               ABS                                                                               POM                                                                               A   B   [° C.]                                                                        [° C.]                                                                        [° C.]                                                                     [sec]                                                                              *1                                __________________________________________________________________________     Example 11                                                                            ◯                                                                     ◯                                                                    ◯                                                                     ◯                                                                     ◯                                                                      ◯                                                                      78    119   None                                                                              20  Absent                            Example 12                                                                            ◯                                                                     ◯                                                                    ◯                                                                     ◯                                                                     ◯                                                                      ◯                                                                      72    116   None                                                                              50  Absent                            Example 13                                                                            ◯                                                                     ◯                                                                    ◯                                                                     ◯                                                                     ◯                                                                      ◯                                                                      74    116   None                                                                              25  Absent                            Example 14                                                                            ◯                                                                     ◯                                                                    ◯                                                                     ◯                                                                     ◯                                                                      ◯                                                                      69    116   None                                                                              25  Absent                            Example 15                                                                            ◯                                                                     ◯                                                                    ◯                                                                     ◯                                                                     ◯                                                                      ◯                                                                      75    117   None                                                                              30  Absent                            Comp. Ex. 7                                                                           ◯                                                                     ◯                                                                    ◯                                                                     Δ                                                                           Δ                                                                            ×                                                                            77    118   None                                                                              28  Present                           Comp. Ex. 8                                                                           ◯                                                                     ◯                                                                    ◯                                                                     Δ                                                                           Δ                                                                            ×                                                                            77    117   None                                                                              30  Present                           Comp. Ex. 9                                                                           ×                                                                           ◯                                                                    ◯                                                                     ◯                                                                     ×                                                                            Δ                                                                            74    116   None                                                                              31  Absent                            Comp. Ex. 10                                                                          ×                                                                           ×                                                                          ×                                                                           ◯                                                                     Δ                                                                            Δ                                                                            73    115   None                                                                              90  Absent                            Comp. Ex. 11                                                                          Δ                                                                           Δ                                                                          Δ                                                                           Δ                                                                           Δ                                                                            Δ                                                                            72    116   25 75  Absent                            Comp. Ex. 12                                                                          ×                                                                           ×                                                                          ×                                                                           ×                                                                           ×                                                                            ×                                                                            73    116   None                                                                              10  Present                           __________________________________________________________________________      Rubber A: Urethane rubber                                                      Rubber B: Natural rubber                                                       *1: ODP: Ozone depletion potentials (ozone destruction coefficient)       

What is claimed is:
 1. A nonflammable water-repellent/oil-repellent composition consisting essentially of 0.01 to 5.0% by weight a fluorine-containing polymer, 40% by weight or more of a non-flammable perfluoro organic solvent compound, and 40% by weight or more of a flammable organic solvent compound.
 2. The water-repellent/oil-repellent composition according to claim 1 wherein said perfluoro organic compound is a compound having a vapor pressure of 30 Torr or more at 25° C.
 3. The water-repellent/oil-repellent composition according to claim 1 wherein said fluorine-containing polymer contains 40 mole % or more of a monomer of a fluorine-containing vinyl compound selected from the group consisting of fluoroalkyl acrylate, fluoroalkyl methacrylate or fluoroalkyl vinyl ether, and the fluorine-containing vinyl monomer.
 4. The water-repellent/oil-repellent composition according to claim 1 wherein said fluorine-containing polymer is a polymer which comprises a monomer containing a perfluoroalkyl group having a molecular weight more than C₆ F₁₃.
 5. The water-repellent/oil-repellent composition according to claim 1 wherein said perfluoro organic compound is at least one selected from the group consisting of perfluroalkanes, perfluorocycloalkanes and perfluoro cyclic ethers.
 6. A The water-repellent/oil-repellent composition according to claim 5 wherein said perfluroalkanes and perfluorocycloalkanes are selected from the group consisting of C₅ F₁₂, C₆ F₁₄, C₇ F₁₆, C₈ F₁₈, C₆ F₁₂, C₇ F₁₄ and C₈ F₁₆.
 7. The water-repellent/oil-repellent composition according to claim 5 wherein said perfluoro cyclic ethers are selected from the group consisting of C₆ F₁₂ O, C₇ F₁₄ O and C₈ F₁₆ O. 